U.S. patent application number 14/340141 was filed with the patent office on 2014-11-13 for transition metal hexacyanometallate electrode with water-soluble binder.
The applicant listed for this patent is Sharp Laboratories of America, Inc.. Invention is credited to Yuhao Lu, Sean Vail, Long Wang.
Application Number | 20140335409 14/340141 |
Document ID | / |
Family ID | 51864999 |
Filed Date | 2014-11-13 |
United States Patent
Application |
20140335409 |
Kind Code |
A1 |
Wang; Long ; et al. |
November 13, 2014 |
Transition Metal Hexacyanometallate Electrode with Water-soluble
Binder
Abstract
A method is provided for fabricating a transition metal
hexacyanometallate (TMHCM) electrode with a water-soluble binder.
The method initially forms an electrode mix slurry comprising TMHCF
and a water-soluble binder. The electrode mix slurry is applied to
a current collector, and then dehydrated to form an electrode. The
electrode mix slurry may additionally comprise a carbon additive
such as carbon black, carbon fiber, carbon nanotubes, graphite, or
graphene. The electrode is typically formed with TMHCM greater than
50%, by weight, as compared to a combined weight of the TMHCM,
carbon additive, and binder. Also provided are a TMHCM electrode
made with a water-soluble binder and a battery having a TMHCM
cathode that is made with a water-soluble binder.
Inventors: |
Wang; Long; (Vancouver,
WA) ; Lu; Yuhao; (Vancouver, WA) ; Vail;
Sean; (Vancouver, WA) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Sharp Laboratories of America, Inc. |
Camas |
WA |
US |
|
|
Family ID: |
51864999 |
Appl. No.: |
14/340141 |
Filed: |
July 24, 2014 |
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14320352 |
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14340141 |
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Current U.S.
Class: |
429/217 ;
427/122; 427/58; 429/218.1; 429/221; 429/226; 429/231.1; 429/231.6;
429/231.8; 429/231.9 |
Current CPC
Class: |
H01M 4/136 20130101;
H01M 4/622 20130101; Y02P 70/50 20151101; H01M 10/052 20130101;
H01M 4/58 20130101; Y02E 60/10 20130101; H01M 4/625 20130101; H01M
4/0404 20130101; H01M 4/1397 20130101 |
Class at
Publication: |
429/217 ;
429/218.1; 429/221; 429/231.8; 429/231.9; 429/226; 429/231.1;
429/231.6; 427/58; 427/122 |
International
Class: |
H01M 4/62 20060101
H01M004/62; H01M 4/04 20060101 H01M004/04; H01M 4/1397 20060101
H01M004/1397; H01M 4/58 20060101 H01M004/58; H01M 4/136 20060101
H01M004/136 |
Claims
1. A transition metal hexacyanometallate, (TMHCM) electrode with
water-soluble binder, the electrode comprising: a current
collector; a TMHCM active material overlying the current collector;
a water-soluble material binding the TMHCM material to the current
collector.
2. The electrode of claim 1 wherein the water-soluble material is
selected from a group consisting of
poly(acrylonitrile,-co-acrylamide)polymer, carboxymethylcellulose
(CMC), poly vinyl alcohol, polyvinylpyrrolidone, poly acrylic acid,
polymethacrylic acid, polyethylene oxide, polyacrylamide,
poly-N-isopropylacrylamide, Poly-N,N-dimethylacrylamide,
polyethyleneimine, polyoxyethylene, polyvinylsulfonic acid,
poly(2-methoxyethoxyethoxyethylene), styrene butadiene rubber
(SBR), butadiene,-acrylonitrile, rubber (NBR), hydrogenated NBR
(HNBR), epichlorhydrin rubber (CHR), acrylate rubber (ACM),
poly(allylamine), xanthan gum, guar gum, chitosan, polyvinyl
acetate, gelatin, casein, cellulose, and poly(carboxylic acid).
3. The electrode of claim 2 wherein the cellulose is selected from
a group consisting of natural cellulose, physically modified
cellulose, chemically modified cellulose, natural polysaccharides,
chemically modified polysaccharides, physically modified
polysaccharides, hydroxy methyl cellulose, and methyl ethyl hydroxy
cellulose.
4. The electrode of claim 2 wherein the poly(carboxylic acid) is
selected from a group consisting of polylactic acid (PLA),
polyacrylic acid, polysuccinic acid, poly maleic acid and
anhydride, poly furoic (pyromucic acid), poly fumaric acid, poly
sorbic acid, poly linoleic acid, poly linolenic acid, poly glutamic
acid, poly methacrylic acid, poly licanic acid, poly glycolic acid,
poly aspartic acid, poly amic acid, poly formic acid, poly acetic
acid, poly propoionic acid, poly butyric acid, poly sebacic acid,
and copolymers thereof.
5. The electrode of claim 1 further comprising: a carbon additive
selected from a group consisting of carbon black, carbon fiber,
carbon nanotubes, graphite, and graphene.
6. The electrode of claim 5 wherein the TMHCM active material is
greater than 50%, by weight, as compared to a combined weight of
the TMHCM active material, carbon additive, and binder.
7. The electrode of claim 1 wherein the TMHCM active material is
expressed by the formula
A.sub.NM1.sub.PM2.sub.Q(CN).sub.R..sub.FH.sub.2O; where "A" is
selected from a first group of metals selected from a group
including alkali and alkaline earth metals; where M1 and M2 are
independently selected from a second group of transition metals;
where N is in a range of 0 to 2; where P is less than or equal to
2; where F is in a range of 0 to 20; where Q is less than or equal
to 2; and, where R is less than or equal to 6.
8. The electrode of claim 7 wherein the first group of metals
includes lithium (Li), sodium (Na), potassium (K), rubidium (Rb),
cesium (Cs), calcium (Ca), strontium (Sr), barium (Ba), silver
(Ag), aluminum (Al), magnesium (Mg), and combinations thereof.
9. The electrode of claim 7 wherein M1 and M2 are each
independently selected from the second group of metals consisting
of titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron
(Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), niobium
(Nb), ruthenium (Ru), tin (Sn), indium (In), cadmium (Cd), Ca, Mg,
strontium (Sr), and barium (Ba).
10. A method of fabricating a transition metal hexacyanometallate
(TMHCM) electrode with a water-soluble binder, the method
comprising: forming an electrode mix slurry comprising TMHCF and a
water-soluble binder; applying the electrode mix slurry to a
current collector; and, dehydrating the electrode mix to form an
electrode.
11. The method of claim 10 wherein forming the electrode mix slurry
includes forming an electrode mix slurry additionally comprising a
carbon additive selected from a group consisting of carbon black,
carbon fiber, carbon nanotuhes, graphite, and graphene.
12. The method of claim 11 wherein forming the electrode includes
forming the electrode with TMHCM greater than 50%, by weight, as
compared to a combined weight of the TMHCM, carbon additive, and
binder.
13. The method of claim 10 wherein forming the electrode mix slurry
includes the water-soluble material being selected from a group
consisting of poly(acrylonitrile-co-acrylamide)polymer,
carboxymethylcellulose (CMC), poly vinyl alcohol,
polyvinylpyrrolidone, poly acrylic acid, polymethacrylic acid,
polyethylene oxide, polyacrylamide, poly-N-isopropylacrylamide,
Poly-N,N-dimethylacrylamide, polyethyleneimine, polyoxyethylene,
polyvinylsulfonic acid, poly(2-methoxyethoxyethoxyethylene),
styrene butadiene rubber (SBR), butadiene-acrylonitrile, rubber
(NBR), hydrogenated NBR. (HNBR), epichlorhydrin rubber (CHR),
acrylate rubber (ACM), poly(allylamine), xanthan gum, guar gum,
chitosan, polyvinyl acetate, gelatin, casein, cellulose, and
poly(carboxylic acid),
14. The method of claim 13 wherein the cellulose is selected from a
group consisting of natural cellulose, physically modified
cellulose, chemically modified cellulose, natural polysaccharides,
chemically modified polysaccharides, physically modified
polysaccharides, hydroxy methyl cellulose, and methyl ethyl hydroxy
cellulose.
15. The method of claim 13 wherein the poly(carboxylic acid) is
selected from a group consisting of polylactic acid (PLA),
polyacrylic acid, polysuccinic acid, poly maleic acid and
anhydride, poly furoic (pyromucic acid), poly fumaric acid, poly
sorbic acid, poly linoleic acid, poly linolenic acid, poly glutamic
acid, poly methacrylic acid, poly licanic acid, poly glycolic acid,
poly aspartic acid, poly amic acid, poly formic acid, poly acetic
acid, poly propoionic acid, poly butyric acid, poly sebacic acid,
and copolymers thereof.
16. A battery having a transition metal hexacyanometallate (TMHCM)
cathode with water-soluble binder, the battery comprising: a
cathode comprising TMHCM and a water-soluble binder; an anode; and,
an electrolyte.
17. The battery of claim 16 wherein the water-soluble binder is
selected from a group consisting of
poly(acrylonitrile,-co-acrylamide)polymer, carboxymethylcellulose
(CMC), poly vinyl alcohol, polyvinylpyrrolidone, poly acrylic acid,
polymethacrylic acid, polyethylene oxide, polyacrylamide,
poly-N-isopropylacrylamide, Poly-N,N-dimethylacrylamide,
polyethyleneinnne, polyoxyethylene, polyvinylsulfonic acid,
poly(2-methoxyethoxyethoxyethylene), styrene butadiene rubber
(SBR), butadiene-acrylonitrile, rubber (NBR), hydrogenated NBR
(HNBR), epichlorhydrin rubber (CHR), acrylate rubber (ACM),
poly(allylamine), xanthan gum, guar gum, chitosan, polyvinyl
acetate, gelatin, casein, cellulose, and poly(carboxylic acid).
18. The battery of claim 17 wherein the cellulose is selected from
a group consisting of natural cellulose, physically modified
cellulose, chemically modified cellulose, natural polysaccharides,
chemically modified polysaccharides, physically modified
polysaccharides, hydroxy methyl cellulose, and methyl ethyl hydroxy
cellulose.
19. The battery of claim 17 wherein the poly(carboxylic acid) is
selected from a group consisting of polylactic acid (PLA),
polyacrylic acid, polysuccinic acid, poly maleic acid and
anhydride, poly furoic (pyromucic acid), poly fumaric acid, poly
sorbic acid, poly linoleic acid, poly linolenic acid, poly glutamic
acid, poly methacrylic acid, poly licanic acid, poly glycolic acid,
poly aspartic acid, poly amic acid, poly formic acid, poly acetic
acid, poly propoionic acid, poly butyric acid, poly sebacic acid,
and copolymers thereof.
20. The battery of claim 16 wherein the cathode further comprises a
carbon additive selected from a group consisting of carbon black,
carbon fiber, carbon nanotubes, graphite, and graphene.
21. The battery of claim 16 wherein the TMHCM is expressed by the
formula A.sub.NM1.sub.PM2.sub.Q(CN).sub.R..sub.FH.sub.2O; where "A"
is selected from a first group of metals selected from a group
including alkali and alkaline earth metals; where M1 and M2 are
independently selected from a second group of transition metals;
where N is in a range of 0 to 2; where P is less than or equal to
2; where F is in a range of 0 to 20; where Q is less than or equal
to 2; and, where R is less than or equal to 6.
22. The battery of claim 16 wherein the anode is made from a
material selected from a group consisting of carbonaceous
materials, alkali metals, alkaline earth metals, alloys including
tin, alloys including lead, alloys including silicon, alloys
including phosphorous, alloys including germanium, titanates
including alkali metals, titanates including alkaline earth metals,
and combinations thereof.
Description
RELATED APPLICATIONS
[0001] This application is a Continuation-in-Part of an application
entitled, ELECTROLYTE ADDITIVES FOR TRANSITION METAL CYANOMETALLATE
ELECTRODE STABILIZATION, invented by Yuhao Lu et al, Ser. No.
14/320,352, filed Jun. 30, 2014, attorney docket No. SLA3431;
[0002] Ser. No. 14/320,352 claims the benefit of a Provisional
application entitled, HARD CARBON COMPOSITE FOR ALKALI METAL-ION
BATTERIES, invented by Yuhao Lu et al, Ser. No. 62/009,069, filed
Jun. 6, 2014, attorney docket No. SLA3416P;
[0003] Ser. No. 14/320,352 claims the benefit of a Provisional
application entitled, METAL CYANOMETALLATE SYNTHESIS METHOD,
invented by Long Wang et al, Ser. No. 62/008,869, filed Jun. 6,
2014, attorney docket No. SLA3430P;
[0004] Ser. No. 14/320,352 is a Continuation-in-Part of an
application entitled, RECHARGEABLE METAL-ION BATTERY WITH
NON-AQUEOUS HYBRID ION ELECTROLYTE, invented by Long Wang et al,
Ser. No. 14/271,498, filed May 7, 2014, attorney docket No.
SLA3388;
[0005] which is a Continuation-in-Part of an application entitled,
REACTIVE SEPARATOR FOR A METAL-ION BATTERY, invented by Long Wang
et al, Ser. No. 14/230,882, filed Mar. 31, 2014, attorney docket
No. SLA3370;
[0006] which is a Continuation-in-Part of an application entitled,
NASICON-POLYMER ELECTROLYTE STRUCTURE, invented by Long Wang et al,
Ser. No. 14/198,755, filed Mar. 6, 2014, attorney docket No.
SLA3367;
[0007] which is a Continuation-in-Part of an application entitled,
BATTERY WITH AN ANODE PRELOADED WITH CONSUMABLE METALS, invented by
Yuhao Lu et al, Ser. No. 14/198,702, filed Mar. 6, 2014, attorney
docket No. SLA3364;
[0008] which is a Continuation-in-Part of an application entitled,
BATTERY ANODE WITH PRELOADED METALS, invented by Long Wang et al,
Ser. No. 14/198,663, filed Mar. 6, 2014, attorney docket No.
SLA3363;
[0009] which is a Continuation-in-Part of an application entitled,
METAL BATTERY ELECTRODE WITH PYROLYZED COATING, invented by Yuhao
Lu et al, Ser. No. 14/193,782, filed Feb. 28, 2014, attorney docket
No. SLA3353;
[0010] which is a Continuation-in-Part of an application entitled,
METAL HEXACYANOMETALLATE ELECTRODE WITH SHIELD STRUCTURE, invented
by Yuhao Lu et al, Ser. No. 14/193,501, filed Feb. 28, 2014,
attorney docket No. SLA3352;
[0011] which is a Continuation-in-Part of an application entitled,
CYANOMETALLATE CATHODE BATTERY AND METHOD FOR FABRICATION, invented
by Yuhao Lu et al, Ser. No. 14/174,171, filed Feb. 6, 2014,
attorney docket No. SLA3351;
[0012] This application is a Continuation-in-Part of an application
entitled, SODIUM IRON(II)-HEXACYANOFERRATE(II) BATTERY ELECTRODE
AND SYNTHESIS METHOD, invented by Yuhao Lu et al, Ser. No.
14/067,038, filed Oct. 30, 2013, attorney docket No. SLA3315;
[0013] which is a Continuation-in-Part of an application entitled,
TRANSITION METAL HEXACYANOMETALLATE-CONDUCTIVE POLYMER COMPOSITE,
invented by Sean Vail et al., Ser. No. 14/059,599, filed Oct. 22,
2013, attorney docket No. SLA3336;
[0014] which is a Continuation-in-Part of an application entitled,
METAL-DOPED TRANSITION METAL HEXACYANOFERRATE (TMHCF) BATTERY
ELECTRODE, invented by Yuhao Lu et al., Ser. No. 13/907,892, filed
Jun. 1, 2013, attorney docket No. SLA3287;
[0015] which is a Continuation-in-Part of an application entitled,
HEXACYANOFERRATE BATTERY ELECTRODE MODIFIED WITH FERROCYANIDES OR
FERRICYANIDES, invented by Yuhao Lu et al., Ser. No. 13/897,492,
filed May 20, 2013, attorney docket No. SLA3286;
[0016] which is a Continuation-in-Part of an application entitled,
PROTECTED TRANSITION METAL HENACYANOFERRATE BATTERY ELECTRODE,
invented by Yuhao Lu et al., Ser. No. 13/872,673, filed Apr. 29,
2013, attorney docket No. SLA3285;
[0017] which is a Continuation-in-Part of an application entitled,
TRANSITION METAL HENACYANOFERRATE BATTERY CATHODE WITH SINGLE
PLATEAU CHARGE/DISCHARGE CURVE, invented by Yuhao Lu et al., Ser.
No. 13/752,930, filed Jan. 29, 2013, attorney docket No.
SLA3265;
[0018] which is a Continuation-in-Part of an application entitled,
SUPERCAPACITOR WITH HEXACYANOMETALLATE CATHODE, ACTIVATED CARBON
ANODE, AND AQUEOUS ELECTROLYTE, invented by Yuhao Lu et al., Ser.
No. 13/603,322, filed Sep. 4, 2012, attorney docket No.
SLA3212.
[0019] Ser. No. 13/752,930 is also a Continuation-in-Part of an
application entitled, IMPROVEMENT OF ELECTRON TRANSPORT IN
HEXACYANOMETALLATE ELECTRODE FOR ELECTROCHEMICAL APPLICATIONS,
invented by Yuhao Lu et al., Ser. No. 13/523,694, filed Jun. 14,
2012, attorney docket No. SLA3152;
[0020] which is a Continuation-in-Part of an application entitled,
ALKALI AND ALKALINE-EARTH ION BATTERIES WITH HEXACYANOMETALLATE
CATHODE AND NON-METAL ANODE, invented by Yuhao Lu et al., Ser. No.
13/449,195, filed Apr. 17, 2012, attorney docket no. SLA3151;
[0021] which is a Continuation-in-Part of an application entitled,
ELECTRODE FORMING PROCESS FOR METAL-ION BATTERY WITH
HEXACYANOMETALLATE ELECTRODE, invented by Yuhao Lu et al., Ser. No.
13/432,993, filed Mar. 28, 2012, attorney docket no. SLA3146, All
these applications are incorporated herein by reference.
BACKGROUND OF THE INVENTION
[0022] 1. Field of the Invention
[0023] This invention generally relates to electrochemical
batteries and, more particularly, to a water-soluble binder for use
with a transition. metal hexacyanometallate electrode.
[0024] 2. Description of the Related Art
[0025] Transition metal cyanometallates (TMCMs) with large
interstitial spaces have been investigated as the cathode material
for rechargeable lithium-ion batteries [1, 2], sodium-ion batteries
[3, 4], and potassium-ion batteries [5]. With an aqueous
electrolyte containing the proper alkali-ions or ammonium-ions,
copper and nickel hexacyanoferrates ((Cu,Ni)-HCFs) exhibited a very
good cycling life with 83% capacity retained after 40,000 cycles at
a charge/discharge current of 17 C (1 C=150 milliamps per gram)
[6-8]. However, the materials within the aqueous electrolyte
demonstrated low capacities and energy densities because: (1) just
one sodium-ion can be inserted/extracted into/from per Cu-HCF or
Ni-HCF formula, and (2) these transition metal cyanoferrate
(TM-HCF) electrodes must be operated below 1.23 V due to the water
electrochemical window. The electrochemical window of a substance
is the voltage range between which the substance is neither
oxidized nor reduced. This range is important for the efficiency of
an electrode, and once out of this range, water becomes
electrolyzed, spoiling the electrical energy intended for another
electrochemical reaction.
[0026] To correct these shortcomings, manganese hexacyanoferrate
(Mn-HCF) and iron hexacyanoferrate (Fe-HCF) were used as cathode
materials in non-aqueous electrolyte [9, 10]. Assembled with a
sodium-metal anode, Mn-HCF and Fe-HCF electrodes cycled between
2.0V and 4.2 V and delivered capacities of about 150 mAh/g.
[0027] Unlike conventional lithium-ion battery cathode materials,
TMHCF can be easily prepared via precipitation in water, and does
not require further high-temperature treatment. Parent applications
Ser. Nos. 62/008,869 and 14/067,038, among others, describe
exemplary precipitation synthesis, and are incorporated herein by
reference. For example, Na.sub.2MnFe(CN).sub.6 can be easily made
by mixing two water solutions containing Na.sub.4Fe(CN).sub.6 and
MnCl.sub.2, which are subsequently filtered and dried at
100.degree. C. Such an aqueous solution-based synthesis route
provides an as-prepared TMHCF chemical having good stability and
dispersion capability in water. Thus, TMHCM has a significantly
lower synthesis cost as compared with the cathode materials used
for lithium-ion batteries (LIBs). The low material cost of TMHCM
makes it a very promising cathode material for stationary energy
storage batteries, but the fabrication costs need to be cut even
further to make it a truly viable battery option. Polyvinylidene
fluoride (PVDF) is used as a standard binder for cathode electrode
in LIBs because of its good adhesion and electrochemical stability.
However, harmful organic solvents, like N-Methyl-2-pyrrolidone
(NMP), are used to dissolve PVDF during the electrode coating
process. A solvent recycling system is therefore required for cost
and environment concerns. Thus, a high fabrication cost is
associated with the conventional PVDF binder.
[0028] In contrast, a water-soluble binder is relatively
inexpensive, process preferable, and environment friendly, all of
which makes it a desirable binder for use in energy storage
batteries. Although the substitution of PVDF with a water-soluble
binder like carboxymethylcellulose (CMC) in LIBs has been
investigated, challenges remain because the electrochemical
performance of lithium transition metal oxides are compromised from
dissolution or poor dispersion capability when aqueous binders are
used. The electrode materials for lithium-ion batteries are
prepared using high temperature calcinations, and problems
typically occur when they are put into a water solution during
electrode fabrication. For example, an ion-exchange reaction occurs
between proton and lithium ions when LiMn.sub.2O.sub.4 is put into
water. In other examples, the dissolution of active materials is
observed when a LiNi.sub.1/3Co.sub.1/3Mn.sub.1/3O2 electrode is
processed in an aqueous solution, and poor adhesion between
LiFePO.sub.4 electrode and the current collector also hinders using
water-soluble binders for battery fabrication.
[0029] It would be advantageous if a high quality electrode could
be fabricated, with transition metal hexacyanometallate (TMHCM) as
an active material and an aqueous binder, for use in sodium-ion
batteries (SIBs) or other rechargeable metal-ion batteries.
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SUMMARY OF THE INVENTION
[0040] Disclosed herein is an electrode comprising transition metal
hexacyanometallates (TMHCMs) as an active material and a
water-soluble binder. The electrode can serve either as a cathode
or an anode in a rechargeable using metal-ions such as lithium
(Li.sup.+), ammonium (NH.sub.4.sup.+), sodium (Na.sup.+), potassium
(K.sup.+), magnesium (Mg.sup.2+), aluminum (Al.sup.3+), cesium
(Cs.sup.+), rubidium (Rb.sup.+), zinc (Zn.sup.2+), barium
(Ba.sup.2+), strontium (Sr.sup.2+), or calcium (Ca.sup.2+) battery.
The water-soluble binder may be
poly(acrylonitrile-co-acrylamide)polymer, carboxymethylcellulose
(CMC), poly vinyl alcohol, polyvinylpyrrolidone, poly acrylic acid,
polymethacrylic acid, polyethylene oxide, polyacrylamide,
poly-N-isopropylacrylamide, Poly-N,N-dimethylacrylamide,
polyethyleneimine, polyoxyethylene, polyvinylsulfonic acid,
poly(2-methoxyethoxyethoxyethylene), styrene butadiene rubber
(SBR), butadiene-acrylonitrile, rubber (NBR), hydrogenated NBR
(HNBR), epichlorhydrin rubber (CHR), acrylate rubber (ACM),
poly(allylamine), xanthan gum, guar gum, chitosan, polyvinyl
acetate, gelatin, casein. The water-soluble binder may be natural
cellulose, physically and/or chemically modified cellulose, natural
polysaccharides, chemically and/or physically modified
polysaccharides, hydroxy methyl cellulose or methyl ethyl hydroxy
cellulose. The water-soluble binder may also be a poly(carboxylic
acid), some examples of which include polylactic acid (PLA),
polyacrylic acid, polysuccinic acid, poly maleic acid and
anhydride, poly furoic (pyromucic acid), poly fumaric acid, poly
sorbic acid, poly linoleic acid, poly linolenic acid, poly glutamic
acid, poly methacrylic acid, poly licanic acid, poly glycolic acid,
poly aspartic acid, poly amic acid, poly formic acid, poly acetic
acid, poly propoionic acid, poly butyric acid, poly sebacic acid,
and copolymers thereof.
[0041] Also provided is a method of fabricating such an electrode
with an aqueous solution. A slurry comprising TMHCM and a binder
selected from the aforementioned examples is formed and coated onto
a metal (e.g., aluminum, copper, nickel, etc.) or carbon current
collector. The binder can be either completely or partially
dissolved into water.
[0042] Accordingly, the method for fabricating the TMHCM electrode
with a water-soluble binder initially forms an electrode mix slurry
comprising TMHCF and a water-soluble binder. The electrode mix
slurry is applied to a current collector, and then dehydrated to
form an electrode. The electrode mix slurry may additionally
comprise a carbon additive such as carbon black, carbon fiber,
carbon nanotubes, graphite, or graphene.
[0043] The electrode is typically formed with TMHCM greater than
50%, by weight, as compared to a combined weight of the TMHCM,
carbon additive, and binder.
[0044] Additional details of the above-described method, a TMHCM
electrode made with a water-soluble binder, and battery made using
such an electrode as the cathode are provided below.
BRIEF DESCRIPTION OF THE DRAWINGS
[0045] FIG. 1 is a partial cross-section view of a transition metal
hexacyanometallate (TMHCM) electrode with water-soluble binder.
[0046] FIG. 2 is a partial cross-sectional view of a battery having
a TMHCM cathode with water-soluble binder.
[0047] FIG. 3 is a flowchart describing one example of fabricating
a TMHCM electrode with water-soluble binder.
[0048] FIGS. 4A and 4B are graphs of the rate capability of
Prussian White (PW) electrodes with ca. 70 .mu.m and 100 micron
(.mu.m) thicknesses, respectively.
[0049] FIGS. 5A and 5B are graphs depicting the rate capability of
PW electrodes fabricated with CMC-SBR based binders, at thicknesses
of 40 and 70 .mu.m, respectively.
[0050] FIG. 6 is a flowchart illustrating a method of fabricating a
TMHCM electrode with a water-soluble binder.
DETAILED DESCRIPTION
[0051] FIG. 1 is a partial cross-section view of a transition
metal. hexacyanometallate (TMHCM) electrode with water-soluble
binder. The electrode 100 comprises a current collector 102, which
may be a metal such as aluminum, copper, or nickel, or conductive
carbon material. A TMHCM active material, represented with
reference designator 104, overlies the current collector 102. A
water-soluble material, represented with reference designator 106,
binds the TMHCM material 104 to the current collector 102.
Typically, as shown, the electrode 100 further comprises a carbon
additive represented by reference designator 108. Some examples of
carbon additives 108 include carbon black (soft carbon carbon
fiber, carbon nanotubes, graphite, and graphene.
[0052] Some examples of the water-soluble material 106 include
poly(acrylonitrile-co-acrylamide)polymer, carboxymethylcellulose
(CMC), poly vinyl alcohol, polyvinylpyrrolidone, poly acrylic acid,
polymethacrylic acid, polyethylene oxide, polyacrylamide,
poly-N-isopropylacrylamide, Poly-N,N-dimethylacrylamide,
polyethyleneimine, polyoxyethylene, polyvinylsulfonic acid,
poly(2-methoxyethoxyethoxyethylene), styrene butadiene rubber
(SBR), butadiene-acrylonitrile, rubber (BR), hydrogenated NBR
(HNBR), epichlorhydrin rubber (CHR), acrylate rubber (ACM),
poly(allylamine), xanthan gum, guar gum, chitosan, polyvinyl
acetate, gelatin, casein, cellulose, and poly(carboxylic acid).
[0053] Some explicit examples of cellulose include natural
cellulose, physically modified cellulose, chemically modified
cellulose, natural polysaccharides, chemically modified
polysaccharides, physically modified polysaccharides, hydroxy
methyl cellulose, and methyl ethyl hydroxy cellulose. Some explicit
examples of poly(carboxylic acid) include polylactic acid (PLA),
polyacrylic acid, polysuccinic acid, poly maleic acid and
anhydride, poly furoic (pyromucic acid), poly fumaric acid, poly
sorbic acid, poly linoleic acid, poly linolenic acid, poly glutamic
acid, poly methacrylic acid, poly licanic acid, poly glycolic acid,
poly aspartic acid, poly amic acid, poly formic acid, poly acetic
acid, poly propoionic acid, poly butyric acid, poly sebacic acid,
and copolymers thereof.
[0054] Lithium is a common choice as an active material in
conventional batteries. Lithium compounds are conventionally
prepared with non-aqueous binders such as PVDF. As noted above, an
ion-exchange occurs when these conventional lithium compounds react
with water, causing dissolution and adhesion problems.
Advantageously, since TMHCM materials are prepared in water, the
use of a water-soluble binder does not create the compatibility
issues associated with the use of lithium compounds. TMHCM is
stable and dispersed easily in water. Since TMHCM materials share
many of the same characteristics as conventional lithium compounds,
the prevalent thinking in the industry has been to make TMHCM
electrodes using many of the same processes as lithium batteries,
including the use of non-aqueous binders. Thus, although the use of
water-soluble binders is not unheard of, it is new to the
application of TMHCM electrodes.
[0055] The TMHCM active material 104 of electrode 100 is typically
greater than 50%, by weight, as compared to a combined weight of
the TMHCM active material 104, carbon additive 108, and binder 106.
The TMHCM active material 104 is expressed by the formula
A.sub.NM1.sub.PM2.sub.Q(CN).sub.R ..sub.FH.sub.2O; [0056] where "A"
is typically an alkali or alkaline earth metal; [0057] where M1 and
M2 are independently selected (may be the same or different metals)
from the group of transition metals; [0058] where N is in the range
of 0 to 2; [0059] where P is less than or equal to 2; [0060] where
F is in the range of 0 to 20; [0061] where Q is less than or equal
to 2; and, [0062] where R is less than or equal to 6.
[0063] Some explicit examples of the metals that comprise the "A"
element include lithium (Li), sodium (Na), potassium (K), rubidium
(Rb), cesium (Cs), calcium (Ca), strontium (Sr), barium (Ba),
silver (Ag), aluminum (Al), magnesium (Mg), and combinations
thereof, Some explicit examples of M1 and M2 metals include
titanium (Ti), vanadium (V), chromium (Cr), manganese (Mn), iron
(Fe), cobalt (Co), nickel (Ni), copper (Cu), zinc (Zn), niobium
(Nb), ruthenium (Ru), tin (Sn), indium (In), cadmium (Cd), Ca,
magnesium (Mg), strontium (Sr), and barium (Ba).
[0064] Some examples of transitions metals from which M1 and M2 are
each independently selected include titanium (Ti), vanadium (V),
chromium (Cr), manganese (Mn), iron (Fe), cobalt (Co), nickel (Ni),
copper (Cu), zinc (Zn), niobium (Nb), ruthenium (Ru), tin (Sn),
indium (In), cadmium (Cd), Ca, Mg, strontium (Sr), and barium
(Ba).
[0065] FIG. 2 is a partial cross-sectional view of a battery having
a TMHCM cathode with water-soluble binder. The battery 200
comprises a cathode 100 comprising TMHCM 104 and a water-soluble
binder 106. The cathode 100, which is one example of the type of
electrode described in FIG. 1, is typically formed on a current
collector 102. The battery 200 also comprises an anode 202 and an
electrolyte 204. As shown, the battery may further comprise an
ion-permeable barrier 206. It is also typical that the cathode
further comprises a carbon additive 108, such as carbon black,
carbon fiber, carbon nanotubes, graphite, or graphene.
[0066] As noted above in the description of FIG. 1, the TMHCM 104
can be expressed by the formula
A.sub.NM1.sub.PM2.sub.Q(CN).sub.R..sub.FH.sub.2O;
[0067] where "A" is selected from a first group of metals that
include alkali and alkaline earth metals;
[0068] where M1 and M2 are independently selected from a second
group of transition metals; [0069] where N is in the range of 0 to
2; [0070] where P is less than or equal to 2; [0071] where F is in
the range of 0 to 20; [0072] where Q is less than or equal to 2;
and, [0073] where R is less than or equal to 6.
[0074] The anode 202 may be made from carbonaceous materials,
alkali metals, alkaline earth metals, alloys including tin, alloys
including lead, alloys including silicon, alloys including
phosphorous, alloys including germanium, titanates including alkali
metals, titanates including alkaline earth metals, and combinations
thereof. The materials that may be used as the water-soluble binder
are listed above in the description of FIG. 1, and are not repeated
here in the interest of brevity.
[0075] Some potential liquid electrolytes 204 include dimethyl
carbonate and diethyl carbonate, ethylene carbonate, propylene
carbonate, dimethoxy ethane, and ethylmethyl carbonate. Some
potential polymer (gel) electrolytes 204 include poly(ethylene
oxide) (PEO), poly(acrylonitrile) (PAN), poly(methyl metacrylate)
(PMMA), polyvinyl chloride) (PVC), poly(vinylidene fluoride)
(PVdF), and polyethylene (PE).
[0076] Electrodes, especially cathodes, in lithium-ion batteries
(LIBs) use a conventional polyvinylidene fluoride (PVDF) as a
binder that results in high material and fabrication cost.
Moreover, the use of N-Methyl-2-pyrrolidone (NMP) as solvent during
the electrode coating process has a strong impact on the
environment. However, due the stability and dispersing capability
of TMHCM in an aqueous solution, it is possible to fabricate such
an electrode in a cheap, fast, and environment friendly process.
Electrodes, fabricated using a doctor blade casting method with a
slurry of PVDF binder and NMP solvent, were employed as the
baseline for comparison. Excellent rate capability and good
mechanical properties were obtained from electrodes made from
Na.sub.2MnFe(CN).sub.6 and water-soluble binders (CMC and SBR). The
electrodes were coated onto an aluminum foil with an aqueous
slurry. The electrode made with the water solution did not
negatively impact battery performance when used as a cathode in a
sodium battery. Electrodes with other TMHCMs and water-soluble
binders can be prepared with similar manner and used in other
rechargeable metal-ion batteries.
[0077] FIG. 3 is a flowchart describing one example of fabricating
a TMHCM electrode with water-soluble binder. In Step 300
Na.sub.2MnFe(CN).sub.6 and carbon black are mixed thoroughly, and
in Step 302 a suspension of CMC and SBR is added. In Step 304 water
is then added into the mixture to form a stable ink that is used
for blade-casting in Step 306. After coating the slurry onto an
aluminum foil, Step 308 dries at the desired temperature. The
result is an electrode of Na.sub.2MnFe(CN).sub.6, carbon black, and
aqueous binder formed with a uniform thickness. It should be noted
the sequence of Steps 300, 302, and 304 may be changed as
needed.
[0078] FIGS. 4A and 4B are graphs of the rate capability of
Prussian White (PW) electrodes with ca. 70 .mu.m and 100 micron
(.mu.m) thicknesses, respectively. The two electrodes consist of
80% Na.sub.2MnFe(CN).sub.6, 10% carbon black, and 10% PVDF,
fabricated by using NMP as a process solvent. The electrodes were
evaluated with a half-cell in which sodium metal was used as a
counter electrode. Discharge capacities under varied current
densities were recorded as benchmarks for comparison to electrodes
with water-based binders. In general, a discharge capacity of 130
mAh/g can be obtained at 1 C (1 C=150 milliamps per gram (mA/g))
regardless of the electrode thickness.
[0079] FIGS. 5A and 5B are graphs depicting the rate capability of
PW electrodes fabricated with CMC-SBR based binders, at thicknesses
of 40 and 70 .mu.m, respectively. The electrode composition was
PW:C:CMC:SBR=75:15:5:5 (FIG. 5A) and PW:C:CMC:SBR=88:7:2.5:2.5
(FIG. 5B). The electrode of FIG. 5A comprises 15% carbon and has a
thickness of 40 microns. The electrode of FIG. 5B comprises 7.5%
carbon and has a thickness of 70 microns. The electrodes prepared
with the CMC/SBR (1/1 wt/wt) binder were evaluated in an identical
manner using the two different carbon contents. The electrode with
the high carbon content (15%; FIG. 5A) had an excellent rate
capability, with a discharge capacity of 130 mAh/g when the battery
was discharged at 10 C. It is notable that with a decreased carbon
amount (7%; FIG. 5B) and similar thickness as that of the
PVDF-based electrode, a high reversible capacity of 140 mAh/g was
obtained at 1 C. Thus, no adversely impact was observed by using
CMC/SBR binders, and a better rate capability was achieved.
[0080] FIG. 6 is a flowchart illustrating a method of fabricating a
TMHCM electrode with a water-soluble binder. Although the method is
depicted as a sequence of numbered steps for clarity, the numbering
does not necessarily dictate the order of the steps. It should be
understood that some of these steps may be skipped, performed in
parallel, or performed without the requirement of maintaining a
strict order of sequence. Generally however, the method follows the
numeric order of the depicted steps. The method starts at Step
600.
[0081] Step 602 forms an electrode mix slurry comprising TMHCF and
a water-soluble binder. Step 604 applies the electrode mix slurry
to a current collector. Step 606 dehydrates the electrode mix to
form an electrode. In one aspect, forming the electrode mix slurry
in Step 602 includes the electrode mix slurry additionally
comprising a carbon additive such as carbon black, carbon fiber,
carbon nanotubes, graphite, or graphene. Typically, the electrode
is formed with TMHCM greater than 50%, by weight, as compared to a
combined. weight of the TMHCM, carbon additive, and binder, after
all the water has been removed in Step 606.
[0082] The water-soluble material may be
poly(acrylonitrile-co-acrylamide)polymer, carboxymethylcellulose
(CMC), poly vinyl alcohol, polyvinylpyrrolidone, poly acrylic acid,
polymethacrylic acid, polyethylene oxide, polyacrylamide,
poly-N-isopropylacrylamide, Poly-N,N-dimethylacrylamide,
polyethyleneimine, polyoxyethylene, polyvinylsulfonic acid,
poly(2methoxyethoxyethoxyethylene), styrene butadiene rubber (SBR),
butadiene-acrylonitrile, rubber (NBR), hydrogenated NBR (HNBR),
epichlorhydrin rubber (CHR), acrylate rubber (ACM),
poly(allylamine), xanthan gum, guar gum, chitosan, polyvinyl
acetate, gelatin, casein, cellulose, or poly(carboxylic acid).
[0083] Some examples of cellulose include natural cellulose,
physically modified cellulose, chemically modified cellulose,
natural polysaccharides, chemically modified polysaccharides,
physically modified polysaccharides, hydroxy methyl cellulose, and
methyl ethyl hydroxy cellulose. Some examples of poly(carboxylic
acid) include polylactic acid (PIA), polyacrylic acid, polysuccinic
acid, poly maleic acid and anhydride, poly furoic (pyromucic acid),
poly fumaric acid, poly sorbic acid, poly linoleic acid, poly
linolenic acid, poly glutamic acid, poly methacrylic acid, poly
licanic acid, poly glycolic acid, poly aspartic acid, poly amic
acid, poly formic acid, poly acetic acid, poly propoionic acid,
poly butyric acid, poly sebacic acid, and copolymers thereof.
[0084] A TMHCM electrode made with a water-soluble binder has been
presented. Examples of particular materials and process steps have
been provided to illustrate the invention. However, the invention
is not limited to merely these examples. Other variations and
embodiments of the invention will occur to those skilled in the
art.
* * * * *